Household hypochlorite bleach with stable latex opacifier

ABSTRACT

LIQUID HOUSEHOLD BLEACH HAVING VISUAL OPACITY IS PROVIDED BY THE INCORPORATION INTO THE BLEACH OF A PARTICULARLY PREPARED STYRENE-VINYL ACID COPOLYMER LATEX WHICH IS HIGHLY RESISTANT TO DETERIORATION IN THE BLEACH AND WHICH ENABLES MAINTENANCE OF USEFUL AVAILABLE CHLORINE LEVELS OVER EXTENDED PERIODS OF TIME. THE LATEX IS PREPARED BY INTRODUCTION OF STYRENE MONOMER INTO A PREFORMED AQUEOUS SOLUTION OF THE VINYL ACID AND A NONCATIONIC SURFACTANT.

United States Patent O 3,689,421 HOUSEHOLD HYPOCHLORITE BLEACH WITHSTABLE LATEX OPACIFIER Benjamin R. Briggs, Los Alamitos, Calif.,assignor to Purex Corporation, Ltd., Lakewood, Calif.

No Drawing. Continuation-impart of abandoned application Ser. No.714,449, Mar. 20, 1968. This application Apr. 9, 1971, Ser. No. 132,805

Int. Cl. C01b 11/06 US. Cl. 252-95 11 Claims ABSTRACT OF THE DISCLOSURELiquid household bleach having visual opacity is provided by theincorporation into the bleach of a particularly prepared styrene-vinylacid copolymer latex which is highly resistant to deterioration in thebleach and which enables maintenance of useful available chlorine levelsover extended periods of time. The latex is prepared by introduction ofstyrene monomer into a preformed aqueous solution of the vinyl acid anda noncationic surfactant.

REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of my copending application Ser. No. 714,449, filedMar. 20, 1968, and now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the invention This inventionhas to do with household liquid bleach. The invention is particularlyconcerned with household bleach of the sort ordinarily added todetergent containing water for the purpose of whitening fabrics beingwashed. For the most part, liquid household bleach cornprises a highlyalkaline solution of sodium hypochlorite usually having an appreciableavailable chlorine content and a pH of or more. More recently, othersources of hypochlorite ion have been developed, primarily for solidbleaches sold in tablet form. Such materials e.g., trichlorocyanuratesmay, however, be sold as liquid bleaches and may take advantage of thepresent invention.

Liquid household bleaches now on the market are watery-appearing,slightly tinted fluids. It has been found that consumer reaction is lessfavorable to watery products than to equally effective products whichhave a degree of body giving them an appearance of greater substance.

(2) Prior art In the liquid detergent field, finely particulate resinsare added to the aqueous or alcoholic detergent solution to impartvisual opacity and pleasing body and coloration.

Attempts to opacify liquid household bleach have not been successful inthe past because of instability of the opacifying resin latex in theharsh environment presented by liquid bleach. Great alkalinity, combinedwith the presence of chlorine ion appears to destroy the latex throughdecomposition of the resin or of the emulsifying agents. Thus, evenresins having known stability to chlorine-containing solutions, such aspolystyrene, have not proved useful as opacifiers, because of theinability of the polymer to remain dispersed in the bleach solution fora period of time equal to storage, shipping and shelf time, expectablyencountered in the normal marketing of bleach. Concomitantly, thechlorine in reacting reduces the available chlorine in the bleach overtime to an unacceptably low level for bleaching utility.

In US. Pat. 3,393,153, a fluorescent bleach is taught to require thepresence of a stabilizer for the fluorescent agent. Suitable stabilizersare inorganic or organic and these are taught to opacity the bleach, theeffect of such stabilizers on available chlorine levels is not noted inthe patent.

SUMMARY OF THE INVENTION It is a major objective of the presentinvention to provide liquid household bleach stably opacified for a moresubstantial and attractive appearance, and which retains its availablechlorine at an acceptable level over time.

Accordingly, there is provided a liquid household bleach comprising anaqueous, highly alkaline solution containing hypochlorite ion and alatex of finely particulate synthetic organic polymer consistingessentially of a styrene monomer which has been emulsion polymerized atan elevated temperature following addition to an aqueous solution of avinyl acid and a noncationic surfactant. The polymer typically containscopolymerized from 65 to 98 parts of the styrene monomer and 2 to 35 andpreferably 8 to 12 parts of vinyl acid per 100 parts of the polymer, byweight. In general, the polymer is of opacifying size range, e.g. 0.1 to2 microns in average particle size and is present in amounts between0.005 and 5 percent by weight. The styrene component of the polymer maybe styrene per se, i.e. vinyl benzene, or other styrene having up to 12carbon atoms and possibly monohalogen substituted as in chlorostyrene.The vinyl acid component of the polymer may be an a, 13 ethylenicallyunsaturated monocarboxylic acid containing from 3 to 4 carbon atoms,i.e. acrylic or methacrylic acid. From 0.5 to 25 parts by weight of ahydrophilic acrylic acid derivative comonomer may replace acorresponding portion of the styrene component in the polymer, primarilyto increase particle size. These comonomers may be the hydroxyesters,ethers, amides and cyano derivatives of acrylic and methacrylic acids.Preferably from 5 to 10 parts by weight of the hydroxyalkyl derivativeof methacrylic acid in which the alkyl group contains from 1 to 4 carbonatoms is used in replacement of a corresponding portion of the styrenecomponent of the polymer.

The liquid household bleach is, except for the presence of the specifiedopacifier, typical of commercially available products and accordinglywill have a pH of 10 or more and a hypochlorite ion concentration of 1to 10 percent by weight, generally derived from sodium hypochlorite, tohave an initial available chlorine above about 65 gms./ liter.

A noncationic surfactant is used to form the polymer latex. Typicalsurfactants are anionic materials and nonionic polyalkylene oxidederivatives of alkylene glycols or phenols.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid household bleachopacified in accordance with this invention may be any hypochlorite ioncontaining solution containing suflicient free alkali to have a pH of 10and preferably 11.5 and higher, typically from 0.1 to 1.0% by weightfree alkali. Percent concentrations of hypochlorite ion will rangebetween 1 and 10 percent by weight with a practical minimum being 2.5%.Most bleaches fall between 3 and 7% hypochlorite ion, and thisconcentration is most suited to use of the invention. As mentioned abovevarious bleaching agents including the heterocyclic N-chlorimides suchas the following are useful herein:

Trichlorocyanuric acid, dichlorocyanuratic acid and salts thereof suchas the alkali metal salts, e.g. sodium and potassium tri-aciddichlorocyanurates. Other imides are hypochlorite ion generating also inaqueous solution and may be used, e.g. N-chlorosuccinimide,N-chloromalonimide, N-chlorphthalimide and N-chloronaphthalimide.

Other materials are the hydantoins, e.g. the 1,3-dichloro-5, S-dimethylhydantoin, N-monochloro-C,C-dimethyl-hydantoin, methylene bis(N-chloro-C, C-dimethylhydantoin),l,3-dichloro-S-methyl--isobutyldimethylhydantoin, 1,3-dichloro-5-methyl5 ethylhydantoin, 1,3-dichloro-5- methyl-Sn-amylhydantoin and the likeas well as trichloromelamine. Preferred sources of hypochlorite ion arethe water soluble inorganic salts such as lithium, calcium, potassiumand particularly sodium hypochlorite.

The opacifying polymer is a particulate form of a styrene copolymerformed in a critical manner. It has been found that most polymer laticesprepared from a styrene and a vinyl acid within the proportions hereindescribed and with or 'without a termonomer such as a vinyl acid esterare not stable in highly alkaline, liquid bleach compositions.Surprisingly the same proportions of monomers provide vastly differentopacifying benefits depending on the polymerization technique employed.To get useful latices of particulate styrene copolymer for opacifyingbleach it has been found essential to first form a solution of the vinylacid monomer in water and the noncationic surfactant prior to adding thestyrene monomer to the reaction vessel. In this manner a latex havingstyrene copolymer finely dispersed therethrough is obtained which isstable for long periods even at elevated temperatures in liquid housholdbleach and which does not so react with the bleach as to depleteavailable chlorine to unacceptable levels during normal shelf life ofthe bleach.

As the polymer components there may be employed styrene per se or vinylbenzene or a substituted styrene such as vinyl toluene or butyl styrene,i.e. alkyl substituted styrenes in which the alkyl groups contain from 1to 4 carbon atoms such that the styrene monomer contains from 8 to 12carbon atoms, inclusive. Or the styrene monomer may be monohalogen ringsubstituted such as chlorostyrene or bromostyrene. The vinyl acidcomponent may be described generically as a water soluble a, Bethylenically unsaturated monocarboxylic acid. Typically such acids willcontain from 3 to 5 carbon atoms, e.g. acrylic, crotonic, itaconic ormethacrylic acids. The proportions of styrene monomer and vinyl acidmonomer are from 65 to 98 parts styrene and conversely from 2 to 35parts of the vinyl acid per 100 parts by weight of the copolymer.

Polymerization is carried out as hereinafter described to providepolymer particles ranging in size between 0.5 and 2 microns. To achievethis size range, particularly at the higher end thereof, it is oftendesirable to incorporate a third monomer in the polymer. This termonomerwill be a hydrophilic acrylic monomer such as a derivative ofmethacrylic or acrylic acid and free of carboxyl groups. Thus, suchderivatives as the ester, hydroxyester, ether, amide or cyanoderivatives of acrylic or methacrylic acids may be used in amounts offrom 0.5 to 25 parts by Weight and preferably between 5 and parts byweight, in substitution for an equal weight amount of the styrenemonomer, per 100 parts of the final opacifying terpolymer. Specifictermonomers of choice include the hydroxyalkyl esters of methacrylicacid in which the alkyl group contains from 1 to 4 carbon atoms andparticularly hydroxyethyl and hydroxypropyl methacrylate, andacrylamide, methacrylamide, acrylonitrile and methyl vinyl ether.

The monomers just described are emulsion polymerized using conventionalcatalysts, oxidizers or reducers, tem-- peratures and pressures but withthe critical step of first dissolving the water soluble vinyl acid inwater, suitably with the emulsifying surfactant, prior to addition ofthe styrene. If used, the hydrophilic vinyl termonomer should also bepredissolved in water prior to introduction of styrene into the reactionvessel. Apart from the just-mentioned sequence of reactant introduction,the preparation of the polymers useful as opacifiers herein is carriedout as for any other exothermic emulsion polymerization. Thus an aqueoussolution of a suitable surfactant is mixed with the water soluble vinylacid. Thereafter the water insoluble styrene reactant is mixed in andagitated until emulsified as the oil phase. The emulsion is thenmaintained at an elevated temperature through exothermic and/or addedheat in admixture with a suitable catalyst, e.g. and preferably watersoluble persulfates such as ammonium and sodium and potassium persulfateand peroxides, e.g. hydrogen peroxide; and also catalysts such ast-butyl perbenzoate and t-butyl hydroperoxide, as well as other oilsoluble materials such as bisazobutyronitrile and cumene hydroperoxide.Following reaction for the required period and at temperatures betweenF. and boiling the reaction mixture is cooled and neutralized withalkali. The latex may be spray or otherwise dried without loss ofdispersibility or stability in liquid household bleach.

As noted, polymers prepared using conventional procedures and from thesame reactants and proportions are not stable in liquid household bleachand rapidly deteriorate in particle size and appear to disintegrate orreact with the bleach to deplete available chlorine levels. While notwishing to be bound to any particular theory concerning the operation ofthe invention it is believed that the unusual resistance of thepresently disclosed compositions to deterioration in bleach may beattributable to the favoring of reaction of the vinyl acid first in thereactor, followed relatively by the polymerization of the styrenemonomer, resulting in a relative styrene richness at the surface of theobtained polymer beads, and a relative vinyl acid richness at the coreof the beads. Styrene homopolymer is not satisfactory, of course, as ableach opacifier, because it is not capable of stable dispersion in thebleach solution, since it lacks polarity. Suitable surfactants foreffecting emulsion polymerization as described and/or for suspending thefinely particulate polymer in bleach are the noncationic types, i.e.anionic, nonionic or amphoteric. Various of these surfactants will showgreater or less tolerance for the harsh environment of liquid householdbleach, depending on the concentration and pH thereof.

Among suitable surfactants are anionic aromatic compounds, e.g.water-soluble higher alkyl aryl sulfonates particularly those havingfrom 8 to about 15 carbon atoms in the alkyl group. It is preferred touse the higher alkyl benzene sulfonates, although other mononuclear arylnuclei, such as toluene, xylene, or phenol, may be used also. The higheralkyl substituent on the aromatic nucleus may be branched orstraight-chained in structure, examples of such group being nonyl,dodecyl and pentadecyl groups derived from polymers of lowermonoolefins, decyl, keryl, and the like.

Illustrative of suitable aliphatic anionic compounds are the normal andsecondary higher alkyl sulfates, particularly those having about 8 to 15carbons in the fatty alcohol residue, such as lauryl (or coconut fattyalcohol) sulfate. Other suitable members of this class are the sulfuricacid esters of polyhydric alcohols incompletely esterified with higherfatty acids; the oleic acid ester of isethionic acid; the higher fattyacid (e.g. coconut) ethanolamide sulfates; the higher fatty acid amidesof amino alkyl sulfonic acids, e.g. lauric acid amide of taurine; andthe like.

These sulfates and sulfonates are used in the form of theirwater-soluble salts, such as the alkali metal and nitrogen-containing,e.g. lower alkylolamine, salts. Examples are the sodium, potassium,ammonium, isopropanolamine, monoand tri-ethanolamine salts of saidhigher alkyl benzene sulfonate, higher alkyl sulfate and the like.

Typical specific examples are:

The sodium salt of a sulfate ester of an alkylphenoxypoly (ethyleneoxy)ethanol, the ammonium salt of this sulfate ester, sodium methyl oleyltaurate, sodium alkyl naphthalene sulfonate, alkyl acyl sodiumsulfonate, sodium tetraphydronaphthalene sulfonate, sodium alkyl arylsulfonate, alkyl amido sulfate, cocomonoglyceride sulfate,dodecylbenzene sodium sulfonate, dodecylbenzene sulfonic acid,tridecylbenzene sodium sulfonate, fatty alcohol sodium sulfate, sodiumdodecyl diphenyl oxide disulfonate, sulfonated castor oil,polyethoxyalkyl phenol sulfonate triethanolamine salts, sodiumtriethanolamine alkyl aryl sulfonate, magnesium lauryl sulfate,potassium lauryl sulfate, sodium lauryl ether sulfate, ammonium laurylether sulfate, sodium tallow sulfate, dodecylbenzene sodium sulfonate,oleyl methyl tauride, ammonium lauryl sulfate, amide sulfonate, and thelike.

In general, suitable nonionic surfactants include those such as producedby the introduction of alkylene oxide group into an organic hydrophobiccompound or group having an aliphatic or aromatic structure. Thehydrophobic organic group generally contains at least 8 carbon atoms andup to about 30 carbon atoms. Condensed with the hydrophobic group are atleast and preferably up to about 50 alkylene oxide groups. It ispreferred to use the polyoxyethylene condensates derived from ethyleneoxide. It is preferred to use the polyalkylene oxide condensates ofalkyl phenol, such as the polyoxyethylene ethers or alkyl phenols havingan alkyl group of at least about six, and usually about 8 to 12 carbons,and preferably 8 to 9 carbon atoms, and an ethylene oxide ratio (No. ofmoles per phenol) of about 7.5, 8.5, 11.5 or 20, though the number ofethylene oxide groups will be usually from about 8 to 40. The alkylsubstituent on the aromatic nucleus may be di-isobutylene, diamyl,polymerized propylene, dimerized C -C olefin, and the like.

Further suitable nonionics are the polyoxyalkylene esters of organicacids, such as the higher fatty acids, rosin acids, tall oil acids, oracids from the oxidation of petroleum, et cetera. These polyglycolesters will contain usually from about 12 to about 30 moles of ethyleneoxide or its equivalent and about 8 to 22 carbons in the acyl group.Suitable products are refined tall oil condensed with 16 or 20 ethyleneoxide groups, or similar polyglycol esters of lauric, stearic, oleicacids, etc.

Additional nonionic agents are the polyalkylene oxide condensates withhigher fatty acid amides, such as the higher fatty acid primary amides,monoand di-ethanolamides. Suitable agents are coconut fatty acid amidecondensed with about to 50 moles of ethylene oxide. The fatty acyl groupwill have similarly about 8 to 22 carbons, and usually about 10 to 18carbon atoms, in such products. The corresponding sulfonamides may beused also if desired.

Other suitable polyethyl nonionics are the polyalkylene oxide ethers ofhigh aliphatic alcohols. Suitable fatty alcohols having a hydrophobiccharacter, preferably 8 to 22 carbons, are lauryl, myristyl, cetyl,stearyl and oleyl alcohols which may be condensed with an appropriateamount of ethylene oxide, such as at least about 6, and preferably about10 to 30 moles. A typical product is oleyl alcohol condensed with about12, or moles of ethylene oxide. The corresponding higher alkylmercaptans or thio-alcohols condensed with ethylene oxide are suitablein the present invention also. The water-soluble polyoxyethylenecondensates with hydrophobic polyoxypropylene glycols may be employedalso, e.g. the ethylene oxide condensates with condensates of propyleneoxide and propylene glycol.

Further suitable nonionic materials are the higher fatty acidalkanolamides, such as the monoethanolamides, diethauolamides andisopropanolamides wherein the acyl radical has about 10 to 14 carbonatoms and amine oxides. Examples are coconut (or equivalent lauric),capric and myristic diethanolamide, monoethanolamide andisopropanolamide, dodecyl dimethyl amine oxide and dimethylacetoxyalkylamine oxide where alkyl is C11"C14- Generally, thesesurfactants comprise from 0.05 to 10 percent by weight, and preferablyfrom 0.5 to 3% of the reaction mixture and the latex added to the liquidhouse hold bleach.

The invention is illustrated by the following examples, in which allparts are by weight.

6 EXAMPLE 1 (A) Polymer preparation One part of dioctyl ester of sodiumsulfosuccinic acid was dissolved in 750 parts of water. There was addedand dissolved 50 parts of methacrylic acid and 10 parts of hydroxyethylmethacrylate. Following achieving complete solution, 500 parts of vinyltoluene was added. Heat was applied to raise the mixture temperature toF. One-half part sodium persulfate (initiator) and one-tenth part sodiumformaldehyde sulfoxylate (reducing agent) were added. Temperatureincreased to 200 F. Thereafter reaction was completed and the reactionmixture cooled, neutralized with potassium hydroxide and filtered.Polymer particles were in the range of 0.5 to 2 microns in particlesize. The product may be spray dried for subsequent incorporation intodry bleach products.

(B) Liquid bleach opacification One part of the latex obtained in A wasmixed with 100 parts of a 5% aqueous solution of sodium hypochloritehaving a pH of 11.5 to opacify the same. After 3 months at 70 F. thebleach was still opacified.

CONTROL I Example 1 was duplicated but the methacrylic acid was mixedfirst with styrene and then added to the aqueous surfactant solution,followed by heating to polymerize. In part B, the emulsion which hadsimilar size particles and the same milky appearance prior to additionto the bleach as the example emulsion, showed immediate physicaldeterioration and quickly demulsified and settled as a fiocculated massin the holding vessel.

EXAMPLE 2 (A) One part of the dioctyl ester of sodium sulfosuccinic acidwas dissolved in 750 parts of water. There was added 50 parts of acrylicacid and 50 parts of methacrylamide and dissolved. Fifty parts ofstyrene were then added and emulsified with heating to F. and additionof 1 part of ammonium persulfate and one part sodium bisulfite. Onrising of the temperature to -150 F. an additional 450 parts of styreneis added over a two hour period, with the temperature held by cooling at-170 F., followed by cooling to room temperature, neutralization andfilter- (B) The product of A stably opacifies liquid household bleach.

EXAMPLE 3 Parts A and B of Example 1 are duplicated using butyl styrenefor vinyl toluene. A stable opacified bleach is obtained.

EXAMPLE 4 Example 1 is duplicated but omitting addition of thehydroxyethyl methacrylate. A fine latex is obtained which is useful inopacifying bleach. Increased quantities of the latex, relative to thoseused in Example 1 are required to obtain equivalent opacity to Example1.

CONTROL II Example 1 was duplicated but reducing the amount ofmethacrylic acid to 10 parts (0.5%) well below the minimum requiredherein. The latex obtained was stable for only two weeks in the testbleach solution.

EXAMPLE 5 0.2 part of dioctyl ester of sodium sulfosuccinic acid(Aerosol OT) was dissolved in 56.5 parts of soft water. There was addedand dissolved 3.9 parts of methacrylic acid and 4.6 parts of vinylsulfonate. Following complete solution of these monomers, 34.6 parts ofstyrene was added. The reaction mixture was heated to 120 F. 0.22 partof sodium persulfate as initiator and 0.08 part of sodium formaldehydesulforalate (Formopan) were added.

Temperature rose to 190-200 F. Thereafter the reaction was completed,the reaction mixture cooled, neutralized with potassium hydroxide andfiltered. Polymer particles were in the range of 0.1 to 2.0 microns.

EXAMPLE 6 A series of compositions were prepared to compare the productof Example in bleach with a commercial copolymer used for opacifyingbleach (Mortons 13-290) Control III, with an unopacified bleach, ControlIV in terms of stability of bleach over time at an elevated temperature.

Control III comprised 2970 grns. of Purex production bleach and 30 gms.of Mortons E-290 copolymer (described above). Control IV comprised 3000gms. of Purex production bleach. Example 6 comprised 2970 grns. of Purexproduction bleach and 30 gms. of the copolymer prepared in Example 5.One drop of antifoam was added to each mixture.

The mixtures were divided into three portions of 1000 gms. each. Themixtures containing opacifier (Control III and Example 6) were placed inclear bottles, while the unopacified bleach (Control IV) was placed inan opaque blue plastic bleach bottle. Available chlorine tests were runon each sample with these results.

INITIAL AVAILABLE CHLORINE The samples were stored variously at roomtemperature (RT) and at 90 F., and their available chlorine measuredafter one week.

1 WEEK STORAGE Test condition Control III: Avail. Cl (gms./liter) RT66.2

Control IV:

Example 6:

AFTER ONE MONTH STORAGE Control III:

Control IV:

Example 6:

AFTER THREE MONTHS STORAGE Control III:

Control IV:

Example 6:

8 AFTER FOUR MONTHS STORAGE Control III (IE-290): Avail. Cl (gms./liter)1 Trace Control IV: 2

90 43.9 Example 6:

CONTROL V A copolymer of styrene and methacrylic acid prepared in latexform as in Example 1 but to have a particle size of 25 microns and amolecular weight of 2,000,000 is added to bleach. The copolymerimmediately settles. This was attributable to too great particle size inthe latex.

I claim:

1. Liquid household bleach having visual opacity and consistingessentially of an aqueous, highly alkaline solution containing 1 to 10%by weight hypochlorite ion and from 0.05 to 5% by weight of a latex offinely particulate synthetic organic polymer consisting essentially of astyrene monomer containing from 8 to 12 carbon atoms which has beenemulsion polymerized at an elevated temperature following addition to anaqueous solution of an 8 ethylenically unsaturated monocarboxylic acidcontaining from 3 to 5 carbon atoms and a noncationic surfactant, saidpolymer containing copolymerized per parts by weight from '65 to 98parts of the styrene monomer and from 2 to 35 parts by weight of thevinyl acid and having a particle size from 0.1 to 2 microns.

2. Liquid household bleach according to claim 1 in which said styrenemonomer is monohalogen ring substituted.

3. Liquid household bleach according to claim 4 in which said styrenemonomer is vinyl benzene.

4. Liquid household bleach according to claim 1 in which said vinyl acidis acrylic acid.

5. Liquid household bleach according to claim 1 in which said vinyl acidis methacrylic acid.

6. Liquid household bleach according to claim 10 including sodiumhypochlorite as source of hypochlorite 1011.

7. Liquid household bleach according to claim 6 in which said bleach hasa pH above 10.

8. Liquid household bleach according to claim 1 including :also from 0.5to 25 parts of a hydrophilic acrylic comonomer selected from thehydroxyester, ether, amide and cyano derivatives of methacrylic andacrylic acids in substitution of corresponding portion of the styrenemonomer.

9. Liquid household bleach according to claim 8 in which the comonomeris present in an amount between 5 and 10 parts and is an hydroxyalkylester of methacrylic acid in which the alkyl group contains from 1 to 4carbon atoms and said vinyl acid is present in an amount between 8 and12 parts per 100 parts of said polymer.

10. Liquid household bleach composition having visual opacity andadequate levels of available chlorine for four months or more consistingessentially of an aqueous highly alkaline solution containing about 5%by weight hypochlorite ion and about 1% by weight of a latex of a finelyparticulate synthetic organic terpolymer consisting essentially ofstyrene polymerized in a previously prepared aqueous mutual solution ofan acrylic acid having 3 or 4 carbon atoms, an hydroxyalkyl ester ofacrylic acid ormethacrylic acid and an anionic surfactant, saidterpolymer containing copolymerized per 100 parts by weight about 10parts of said acid, about 10 parts of said ester and about 80 partsstyrene.

11. Method of preparing a stable, visually opacified liquid bleachcomposition having adequate levels of available chlorine for four monthsor more by suspension in the bleach of finely particulate styrenecontaining polymer which includes forming latex of a polymer consistingessentially of 65 to 98 parts of a styrene monomer containing 8 to 12carbon atoms inclusive and 2 to 35 parts of acrylic or methacrylic acidby adding the styrene as a monomer to an aqueous solution acidcontaining a surfac- References Cited UNITED STATES PATENTS 3,244,6584/1966 Grosser et al 26029.6 E 3,282,876 11/1966 Williams et a1. 260-296E 3,297,619 1/1967 Bluhm et al 260-296 E 3,393,153 7/1968 Zimmerer et a1252-187 MAYER WEINBLA'IT, Primary Examiner I. GLUCK, Assistant ExaminerU.S. Cl. X.R.

